Microbicidal hydroxyethyl-cyclopropyl-azolyl derivatives

ABSTRACT

A herbicidal hydroxyethyl-cyclopropyl-azolyl derivative of the formula ##STR1## in which R 1  represents halogen, phenyl or the grouping --Z-R 3 , wherein 
     Z represents oxygen, sulphur, SO or SO 2  and 
     R 3  represents alkyl, phenyl or benzyl, 
     R 2  represents alkenyl, optionally substituted furyl, optionally substituted thienyl or the radical of the formula ##STR2##  wherein R 4  represents difluoromethoxy, 1,1,2,2-tetrafluoroethoxy, 1,1,2-trifluoro-2-chloro-ethoxy, cyano, formyl, alkoximinoalkyl, carbalkoxy, dialkoxyalkyl, phenoxyalkyl which is optionally substituted in the phenyl moiety by halogen, or benzyloxy which is optionally substituted in the phenyl moiety by halogen and 
     R 5  represents hydrogen or halogen, or 
     R 4  and R 5  are linked in the ortho-position and together represent --O--CH 2  --O--, or 
     R 2  represents the radical of the formula ##STR3## in which R 6  represents difluoromethoxy, 1,1,2,2-tetrafluoroethoxy or 1,1,2-trifluoro-2-chloro-ethoxy, or 
     R 2  also represents phenyl which is optionally substituted by halogen and/or phenyl if Y represents the grouping ##STR4## X represents nitrogen or a CH group and Y represents the groupings --CH 2  -CH 2  --, --CH═CH--, --C.tbd.C-- or ##STR5## or an acid or metal salt addition product thereof.

This is a division of application Ser. No. 535,266, filed Jun. 8, 1990,now U.S. Pat. No. 5,096,912.

The present invention relates to new hydroxyethyl-cyclopropyl-azolylderivatives, to a number of processes for their preparation and to theiruse as microbicides in plant protection and in the protection ofmaterials.

It is already known that numerous hydroxyalkylazolyl derivatives havefungicidal properties (cf. EP-OS (European Published Specification)0,298,332). Thus, for example,1-(4-trifluoromethoxyphenyl)-3-(1-chloro-cycloprop-1-yl)-4-(1,2,4-triazol-1-yl)-but-1-en-3-oland1-(4-chlorophenyl)-3-(1-chloro-cycloprop-1-yl)-4-(1,2,4-triazol-1-yl)-butan-3-olcan be used for combating phytopathogenic fungi. The activity of thesesubstances is good; however at low application rates the activity insome cases leaves something to be desired.

New hydroxyethyl-cyclopropyl-azolyl derivatives of the formula ##STR6##in which R¹ represents halogen, phenyl or the grouping --Z--R³, wherein

Z represents oxygen, sulphur, SO or SO₂ and

R³ represents alkyl, phenyl or benzyl,

R² represents alkenyl, optionally substituted furyl, optionallysubstituted thienyl or the radical of the formula ##STR7## wherein R⁴represents difluoromethoxy, 1,1,2,2-tetrafluoroethoxy,1,1,2-trifluoro-2-chloro-ethoxy, cyano, formyl, alkoximinoalkyl,carbalkoxy, dialkoxyalkyl, phenoxyalkyl which is optionally substitutedin the phenyl moiety by halogen, or benzyloxy which is optionallysubstituted in the phenyl moiety by halogen and

R⁵ represents hydrogen or halogen, or

R⁴ and R⁵ are linked in the ortho-position and together represent--O--CH₂ --O--, or

R² represents the radical of the formula ##STR8## in which R⁶ representsdifluoromethoxy, 1,1,2,2-tetrafluoroethoxy or1,1,2-trifluoro-2-chloro-ethoxy, or

R² also represents phenyl which is optionally substituted by halogenand/or phenyl if Y represents the grouping ##STR9## X representsnitrogen or a CH group and Y represents the groupings --CH₂ --CH₂ --,--CH═CH--, --C.tbd.C-- or ##STR10## and their acid addition salts andmetal salt complexes have now been found.

The substances according to the invention contain an asymmetricallysubstituted carbon atom. They can therefore be obtained in opticalisomer forms. Moreover, those substances of the formula (I) in which Yrepresents a --CH═CH-- group or a ##STR11## group can also be present inthe form of cis or trans isomers. The invention relates both to theindividual isomers and to their mixtures.

It has furthermore been found that hydroxyethyl-cyclopropyl-azolylderivatives of the formula (I) and their acid addition salts and metalsalt complexes are obtained when

a) oxiranes of the formula ##STR12## in which R¹, R² and Y have theabovementioned meanings, are reacted with azoles of the formula##STR13## in which X has the abovementioned meaning, in the presence ofan acid-binding agent and in the presence of a diluent, or

b) ethanol derivatives of the formula ##STR14## in which R¹, R² and Yhave the abovementioned meanings, and

Hal represents chlorine, bromine or iodine,

are reacted with azoles of the formula ##STR15## in which X has theabovementioned meaning, in the presence of an acid-binding agent and inthe presence of a diluent, or

c) hydroxyethyl-cyclopropyl-azolyl derivatives of the formula ##STR16##in which R¹, R² and X have the abovementioned meanings, are reacted witha reagent suitable for epoxidation, if appropriate in the presence of adiluent,

and, if appropriate, an acid or a metal salt is then adducted to thecompounds of the formula (I) thus obtained.

Finally, it has been found that the new hydroxyethyl-cyclopropyl-azolylderivatives of the formula (I) and their acid addition salts and metalsalt complexes have very good microbicidal properties and can be usedboth in plant protection and also in the protection of materials.

Surprisingly, the substances according to the invention show adistinctly better activity in combating phytopathogenic fungi than1-(4-trifluoromethoxyphenyl)-3-(1-chloro-cycloprop-1-yl)-4-(1,2,4-triazol-1-yl)-but-1-en-oland1-(4-chloro-phenyl)-3-(1-chloro-cycloprop-1-yl)-4-(1,2,4-triazol-1-yl)-butan-3-ol,which are previously known compounds of similar constitution and withthe same type of action.

Formula (I) provides a general definition of thehydroxyethyl-cyclopropyl-azolyl derivatives according to the invention.Preferably, in this formula

R¹ represents fluorine, chlorine, bromine, phenyl or the grouping--Z--R³, wherein

Z represents oxygen, sulphur, SO or SO₂ and

R³ represents alkyl having 1 to 6 carbon atoms, phenyl or benzyl,

R² represents straight-chain or branched alkenyl having 2 to 8 carbonatoms, furyl which is optionally substituted by halogen or furyl,thienyl which is optionally substituted by halogen or the radical of theformula ##STR17## wherein R⁴ represents difluoromethoxy,1,1,2,2-tetrafluoroethoxy, 1,1,2-trifluoro-2-chloro-ethoxy, cyano,formyl, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy groupand 1 to 4 carbon atoms in the alkyl group, carbalkoxy having 1 to 4carbon atoms in the alkoxy group, dialkoxyalkyl having 1 to 4 carbonatoms in each alkoxy group and 1 to 4 carbon atoms in the alkyl group,phenoxyalkyl having 1 to 4 carbon atoms in the alkyl group and which isoptionally substituted in the phenyl moiety by fluorine and/or chlorine;or benzyloxy which is optionally substituted in the phenyl moiety byfluorine and/or chlorine and

R⁵ represents hydrogen, fluorine, chlorine or bromine, or

R⁴ and R⁵ are linked in the ortho-position and together represent--O--CH₂ --O--, or

R² represents the radical of the formula ##STR18## wherein R⁶ representsdifluoromethoxy, 1,1,2,2-tetrafluoroethoxy or1,1,2-trifluoro-2-chloro-ethoxy, or

R² represents phenyl which is optionally substituted by fluorine,chlorine and/or phenyl if Y represents the grouping ##STR19## Xrepresents hydrogen or a CH group and Y represents the groupings --CH₂--CH₂ --, --CH═CH--, --C.tbd.C-- or ##STR20##

Particularly preferred compounds of the formula (I) are those in which

R¹ represents fluorine, chlorine, bromine, phenyl or the grouping--Z--R³, wherein

Z represents oxygen, sulphur, SO or SO₂ and

R³ represents alkyl having to 4 carbon atoms, phenyl or benzyl,

R² represents straight-chain or branched alkenyl having 3 to 6 carbonatoms, furyl which is optionally substituted by fluorine, chlorine,bromine or furyl, thienyl which is optionally substituted by fluorine,chlorine or bromine, or the radical of the formula ##STR21## wherein R⁴represents difluoromethoxy, 1,1,2,2-tetrafluoroethoxy,1,1,2-trifluoro-2-chloro-ethoxy, cyano, formyl, alkoximinoalkyl having 1or 2 carbon atoms in the alkoxy group and 1 or 2 carbon atoms in thealkyl group, carbalkoxy having 1 or 2 carbon atoms in the alkoxy group,dialkoxyalkyl having 1 or 2 carbon atoms in each alkoxy group and 1 or 2carbon atoms in the alkyl group, phenoxyalkyl having 1 or 2 carbon atomsin the alkyl group and optionally substituted in the phenyl moiety byfluorine and/or chlorine or benzyloxy which is optionally substituted inthe phenyl moiety by fluorine and/or chlorine and

R⁵ represents hydrogen, fluorine, chlorine or bromine, or

R⁴ and R⁵ are linked in the ortho-position and together represent--O--CH₂ --O--, or

R² represents the radical of the formula ##STR22## wherein R⁶ representsdifluoromethoxy, 1,1,2,2-tetrafluoroethoxy or1,1,2-trifluoro-2-chloro-ethoxy, or

R² also represents phenyl which is optionally substituted by fluorine,chlorine and/or phenyl if Y represents the grouping ##STR23## Xrepresents nitrogen or a CH group and Y represents the grouping --CH₂--CH₂ --, --CH═CH--, --C.tbd.C-- or ##STR24##

Preferred compounds according to the invention are also additionproducts of acids and those hydroxyethyl-cyclopropyl-azolyl derivativesof the formula (I) in which R¹, R², X and Y have the meanings which havealready been mentioned as being preferred for these radicals.

The acids which can be adducted preferably include hydrohalic acids suchas, for example, hydrochloric acid and hydrobromic acid, in particularhydrochloric acid, and further phosphoric acid, nitric acid, sulphuricacid, mono- and bifunctional carboxylic acids and hydroxycarboxylicacids, such as, for example, acetic acid, maleic acid, succinic acid,furaric acid, tartaric acid, citric acid, salicyclic acid, sorbic acidand lactic acid and also sulphoic acids, such as, for example,p-toluenesulphonic acid, 1,5-naphthalenedisulphonic acid orcamphorsulphonic acid.

Additionally preferred compounds according to the invention are additionproducts of salts of metals of main groups II to IV and subgroups I andII and also IV to VIII of the Periodic Table of the elements and thosehydroxyethyl-cyclopropyl-azolyl derivatives of the formula (I) in whichR¹, R², X and Y have the meanings which have already been mentioned asbeing preferred for these radicals.

In this connection, salts of copper, zinc, manganese, magnesium, tin,iron and nickel are particularly preferred. Suitable anions of thesesalts are those which are derived from those acids which lead tophysiologically tolerated addition products.

Particularly preferred acids of this type in this connection are thehydrohalic acids, such as, for example, hydrochloric acid andhydrobromic acid, and further phosphoric acid, nitric acid and sulphuricacid.

If2-(1-chloro-cycloprop-1-yl)-2-[4-(2-chloro-1,1,2-trifluoro-ethoxy)-phenyl-ethenyl]-oxiranand 1,2,4-triazole are used as starting materials, the course of process(a) according to the invention can be illustrated by the followingequation: ##STR25##

If 1-chloro-2-(1-chloro-cycloprop-1-yl)-4-(thiophen-2-yl)-but-3-in-2-oland 1,2,4-triazole are used as starting materials, the course of process(b) according to the invention can be illustrated by the followingequation: ##STR26##

If4-biphenylyl-2-(1-chloro-cycloprop-1-yl)-1-(1,2,4-triazol-1-yl)-but-3-en-2-olis used as a starting material and 3-chloro-perbenzoic acid as anepoxidation reagent, the course of process (c) according to theinvention can be illustrated by the following equation: ##STR27##

Formula (II) provides a general definition of the oxiranes required asstarting materials for process (a) according to the invention. In thisformula, R¹, R² and Y preferably have those meanings which have alreadybeen mentioned as being preferred for these radicals in connection withthe description of the substances of the formula (I) according to theinvention.

The oxiranes of the formula (II) were hitherto unknown. They can beprepared by a process in which

d) cyclopropyl ketones of the formula ##STR28## in which R¹, R² and Yhave the abovementioned meanings, are reacted either

α) with dimethyloxosulphonium methylide of the formula ##STR29## or β)with dimethylsulphonium methylide of the formula ##STR30## in thepresence of a diluent, or by a process in which

e) carbinols of the formula ##STR31## in which R¹ and R² have theabovementioned meanings and Hal' represents chlorine or bromine,

are reacted with bases in the presence of a diluent.

The cyclopropyl ketones of the formula (V) required as startingmaterials for carrying out process (d) were hitherto unknown. They canbe prepared by a process in which

f) aldehydes of the formula

    R.sup.2 --CHO                                              (VIII)

in which

R² has the abovementioned meaning, are reacted with methyl cyclopropylketones of the formula ##STR32## in which R¹ has the abovementionedmeaning, in the presence of a catalyst and in the presence of a diluentand, if appropriate, the resulting cyclopropyl ketones of the formula##STR33## in which R¹ and R² have the abovementioned meanings, areeither α) hydrogenated in the presence of a catalyst and in the presenceof a diluent, or

β) reacted with a reagent suitable for epoxidation, if appropriate inthe presence of a diluent,

or by a process in which

g) acetylenes of the formula

    R.sup.2 --C.tbd.CH                                         (X)

in which R² has the abovementioned meaning, are reacted with acidhalides of the formula ##STR34## in which R¹ has the abovementionedmeaning and

Hal" represents chlorine or bromine, in the presence of a catalyst andin the presence of a diluent.

The aldehydes of the formula (VIII) required as starting materials inprocess (f) are generally known compounds of organic chemistry.

The methyl cyclopropyl ketones of the formula (IX) additionally requiredas reaction components when carrying out process (f) are known or can beprepared by methods which are known in principle (cf. Synthesis 1977,189).

Suitable catalysts for carrying out the first step of process (f) areall reaction accelerators which are customary for condensations of thistype. Basic substances, for example alkali metal hydroxides, such assodium hydroxide or potassium hydroxide are preferably utilizable.

Suitable diluents for carrying out the first step of process (f) are allinert organic solvents which are customary for reactions of this type.Alcohols, such as methanol, ethanol, isopropanol, n-butanol andtert.-butanol are preferably utilizable.

The reaction temperatures can be varied within a relatively wide rangewhen carrying out the first step of process (f). In general, thereaction is carried out at temperatures between 0° C. and 100° C.,preferably between 10° C. and 80° C.

The first step of process (f) is in general carried out under normalpressure. However, it is also possible to work at elevated or reducedpressure.

When carrying out the first step of process (f), 1 mole of aldehyde ofthe formula (VIII) and a catalytic amount of reaction accelerator areemployed per mole of methyl cyclopropyl ketone of the formula (IX).However it is also possible to use one or the other component in anexcess. Working up is carried out by customary methods. In general, aprocedure is used in which the reaction products obtained in a solidstate are filtered off with suction and are used for the furtherreactions, if necessary after prior purification.

In the second step of process (f), when working according to variant α,the cyclopropyl ketones of the formula (V-a) are hydrogenated withhydrogen in the presence of a catalyst and a diluent. In this case, thereaction is carried out in the liquid phase using a suspendedpulverulent hydrogenation catalyst (heterogeneous) or using a catalystcomplex soluble in the diluent (homogeneous). The hydrogenation can becarried out discontinuously (batchwise) or continuously as liquid-phaseor trickle-phase hydrogenation in known hydrogenation reactors, such asautoclaves, autoclave cascades, tube reactors or recycling reactors. Thepreferred procedure is discontinuous liquid-phase hydrogenation inautoclaves at elevated pressure.

Suitable diluents for carrying out the second step of process (f,variant α) are inert organic solvents. These preferably includealcohols, such as methanol, ethanol, isopropanol or ethylene glycol;ethers, such as diethyl ether, diisopropyl ether, ethylene glycolmonomethyl ether, ethylene glycol dimethyl ether, dioxane ortetrahydrofuran; saturated hydrocarbons, such as n-heptane orcyclohexane; aromatic hydrocarbons, such as toluene; and esters, such asethyl acetate.

The reaction temperatures can be varied within a relatively wide rangewhen carrying out the second step of process (f, variant α). In generalthe reaction is carried out at temperatures between 0° C. and 150° C.,preferably between 20° C. and 120° C.

The hydrogenations in the second step of process (f, variant α) arecarried out at normal pressure or also at elevated pressure. In general,the reaction is carried out under pressures between 1 and 150 bar,preferably between 5 and 60 bar.

Working up takes place by customary methods when carrying out the secondstep of process (f, variant α).

Suitable epoxidation agents for carrying out the second step of process(f, variant β) are all epoxidation reagents suitable for reactions ofthis type. Peracids, such as perbenzoic acid, 3-chloro-perbenzoic acidand peracetic acid, and additionally also hydrogen peroxide, arepreferably utilizable.

Suitable diluents for carrying out the second step of process (f,variant β) are all solvents customary for reactions of this type. If thereaction is carried out with peracids, inert organic solvents, such asdichloromethane, are preferred. If hydrogen peroxide is used as theepoxidation agent, water or mixtures of water and inert organicsolvents, such as dichloromethane, are preferably used.

The reaction temperatures can be varied within a certain range whencarrying out the second step of process (f, variant β). In general, thereaction is carried out at temperatures between 0° C. and 40° C.,preferably between 10° C. and 30° C.

When carrying out the second step of process (f, variant β), a procedureis in general used in which an equivalent amount or, also, an excess ofepoxidation agent is employed per mole of cyclopropyl ketone of theformula (V-a). Working up is carried out by customary methods.

The acetylenes of the formula (X) required as starting substances forcarrying out process (g) are known or can be prepared in a simple mannerby methods which are known in principle.

The acid halides of the formula (XI) required as reaction components forcarrying out process (g) are also known or can be prepared by methodswhich are known in principle.

Suitable catalysts for carrying out process (g) are all reactionaccelerators which are customary for reactions of this type. Coppersalts, such as, for example copper iodide, are preferably utilizable.

Suitable diluents for carrying out process (g) are all inert organicsolvents which are customary for reactions of this type. Ethers such astetrahydrofuran and diethylether, are preferably utilizable.

The reaction temperatures can be varied within a certain range whencarrying out process (g) according to the invention. In general, thereaction is carried out at temperatures between -78° C. and +50° C.,preferably between -78° C. and +40° C.

When carrying out process (g), in general 1 to 1.2 moles of acid halideof the formula (XI) and catalyst are employed per mole of acetylene ofthe formula (X). Working up is carried out by customary methods.

The dimethyl-oxo-sulphonium methylide of the formula (VI) required as areaction component in process (d) is known (cf. J. Am. Chem. Soc. 87,1363-1364 (1965)). It is processed in the above reaction in the freshlyprepared state by generating it in situ by reaction oftrimethyloxosulphonium iodide with sodium hydride or sodium amide, inparticular with potassium tert.-butoxide or sodium methoxide, in thepresence of a diluent.

The dimethylsulphonium methylide of the formula (VII) additionallypossible as a reaction component is also known (cf. Heterocycles 8, 397(1977)). It is also employed in the above reaction in the freshlyprepared state by generating it in situ, for example fromtrimethylsulphonium halide or trimethylsulphonium methylsulphate, in thepresence of a strong base, such as, for example, sodium hydride, sodiumamide, sodium methoxide, potassium tert.-butoxide or potassiumhydroxide, in the presence of a diluent, such as tert.-butanol ordimethyl sulphoxide.

Suitable diluents for carrying out process (d) are inert organicsolvents. Alcohols, such as tert.-butanol, ethers, such astetrahydrofuran or dioxane, and further aliphatic and aromatichydrocarbons, such as benzene, toluene or xylene, and also stronglypolar solvents, such as dimethyl sulphoxide, are preferably utilizable.

The reaction temperatures can be varied within a relatively wide rangewhen carrying out process (d). In general, the reaction is carried outbetween 0° C. and 100° C., preferably between 10° C. and 60° C.

When carrying out process (d), in general 1 to 3 moles ofdimethyloxosulphonium methylide of the formula (VI) or ofdimethylsulphonium methylide of the formula (VII) are employed per moleof cyclopropyl ketone of the formula (V). The isolation of the oxiranesof the formula (II) is carried out by customary methods.

The carbinols of the formula (IV-a) required as starting materials forcarrying out process (e) were hitherto unknown. They can be prepared bya process in which

h) halogenoketones of the formula ##STR35## in which R¹ has theabovementioned meaning and

Hal"' represents chlorine or bromine,

are reacted acetylene salts of the formula

    R.sup.2 --C.tbd.C.sup.⊖ Me⊕                    (XIII)

in which

R² has the abovementioned meaning and

Me represents an equivalent of a metal cation,

if appropriate in the presence of an acid-binding agent and in thepresence of a diluent.

The halogenoketones of the formula (XII) required as starting substancesin process (h) are known (cf. EP-OS (European Published Specification)0,298,332).

Formula (XIII) provides a general definition of the acetylene saltsrequired as reaction components in process (h). In this formula, R²preferably has those meanings which have already been mentioned as beingpreferred for this radical in connection with the description of thesubstances of the formula (I) according to the invention. Me preferablyrepresents a lithium cation or an equivalent of a Cer(III) cation.

The acetylene salts of the formula (XIII) are known or can be preparedby methods which are known in principle.

Suitable acid-binding agents for carrying out process (h) are allcustomary acid acceptors.

Possible diluents for carrying out process (h) are all customary inertorganic solvents. Aromatic hydrocarbons, such as toluene, andadditionally ethers, such as diethyl ether, tetrahydrofuran, tert.-butylmethyl ether and mixtures of these ethers are preferably utilizable.

The reaction temperatures can be varied within a relatively wide rangewhen carrying out process (h). In general, the reaction is carried outat temperatures between -100° C. and +100° C., preferably between -80°C. and +50° C.

Process (h) is in general carried out under normal pressure. However, itis also possible to work at elevated or reduced pressure.

When carrying out process (h), in general 1 to 3 moles of acetylene saltof the formula (XIII) are employed per mole of halogenoketone of theformula (XII). Working up is carried out by customary methods.

Possible bases for carrying out process (e) are all organic andinorganic acid-binding agents customarily suitable for reactions of thistype. Alkali metal carbonates, such as sodium carbonate and potassiumcarbonate, further alkali metal hydroxides, such as sodium hydroxide andpotassium hydroxide, additionally alkali metal alkoxides, such as sodiummethoxide and potassium methoxide and sodium ethoxide and potassiumethoxide and also potassium tert.-butoxide, and furthermore lowertertiary alkylamines, cycloalkylamines and aralkylamines, such as, inparticular, triethylamine, are preferably utilizable.

Possible diluents for carrying out process (e) are all customary inertorganic solvents. Nitriles such as acetonitrile, further aromatichydrocarbons, such as benzene, toluene and dichlorobenzene, additionallyformamides, such as dimethylformamide, and also strongly polar solvents,such as dimethyl sulphoxide and hexamethylphosphoramide are preferablyutilizable.

The reaction temperatures can be varied within a certain range whencarrying out process (e). In general, the reaction is carried out attemperatures between -20° C. and +100° C., preferably between 0° C. and60° C.

When carrying out process (e), the reaction is in general carried outunder normal pressure. However, it is also possible to work at elevatedor reduced pressure.

When carrying out process (e) in general 1 to 3 moles of base areemployed per mole of carbinol of the formula (VI-a). Working up iscarried out by customary methods.

The azoles of the formula (III) required as reaction components inprocess (a) according to the invention are generally known compounds oforganic chemistry.

Suitable acid-binding agents for carrying out process (a) according tothe invention are all customary acid acceptors. Alkali metal carbonatesand hydrogen carbonates, such as sodium carbonates, potassium carbonateor sodium hydrogen carbonate, further alkali metal hydroxides andalkoxides, such as sodium hydroxide, potassium hydroxide, sodiummethoxide or potassium tert.-butoxide, additionally tertiary aliphaticor aromatic amines, such as triethylamine, N,N-dimethyl-cyclohexylamine,N,N-dimethyl-benzylamine and pyridine, and additionally cyclic amines,such as1,5-diaza-bicyclo[4.3.0]non-5-ene(DBN),1,8-diaza-bicyclo[5.4.0]undec-7-ene(DBU)and 1,4-diaza-bicyclo[2.2.2]octane (DABCO) are preferably utilizable.

Possible diluents for carrying out process (a) according to theinvention are all customary inert organic solvents. Nitriles, such as,in particular, acetonitrile; aromatic hydrocarbons, such as benzene,toluene and dichlorobenzene; formamides, such as, in particular,dimethylformamide, and also hexamethylphosphoramide are preferablyutilizable.

The reaction temperatures for carrying out process (a) according to theinvention can be varied within a relatively wide range. In general, thereaction is carried out at temperatures between 0° C. and 200° C.,preferably between 50° and 150° C.

When carrying out process (a) according to the invention, 1 to 4 molesof azole of the formula (III) and 1 to 2 moles of base are preferablyemployed per mole of oxirane of the formula (II). The isolation of thefinal products is carried out in a customary manner.

Formula (IV) provides a general definition of the ethanol derivativesrequired as starting substances for carrying out process (b) accordingto the invention. In this formula, R¹, R² and Y preferably have thosemeanings which have already been mentioned as being preferred for theseradicals in connection with the description of the substances of theformula (I) according to the invention.

The ethanol derivatives of the formula (IV) were hitherto unknown. Theycan be prepared by process (h) if they are those substances in which Yrepresents --C.tbd.C--. The other ethanol derivatives of the formula(IV) can be prepared from these substances of the formula (IV-a) bycompletely or partially hydrogenating the triple bond by customarymethods or by epoxidizing those substances in which Y represents--CH═CH-- by customary methods (cf. second step of process (f, variantβ)).

When carrying out process (b) according to the invention, possibleacid-binding agents are all customary acid acceptors. All thoseacid-binding agents which have already been mentioned in connection withthe description of process (a) according to the invention are preferablyutilizable.

Suitable diluents for carrying out process (b) according to theinvention are all customary inert organic solvents. All those diluentswhich have already been mentioned in connection with the description ofprocess (a) according to the invention are preferably utilizable.

The reaction temperatures can be varied within a relatively wide rangewhen carrying out process (b) according to the invention. In general,the reaction is carried out at temperatures between 0° C. and 120° C.,preferably between 20° C. and 100° C.

Process (b) according to the invention is in general carried out undernormal pressure. However, it is also possible to work at elevated orreduced pressure.

When carrying out process (b) according to the invention, 1.5 to 3 molesof azole of the formula (III) and 3 to 6 moles of acid-binding agent arein general employed per mole of ethanol derivative of the formula (IV).Working up is carried out by customary methods.

When carrying out process (c) according to the invention,hydroxyethyl-cyclopropyl-azolyl derivatives of the formula (Ia) areemployed as starting materials. These can be prepared by processes (a)or (b) according to the invention. The epoxidation by process (c)according to the invention is carried out in the same manner as theepoxidation in the second step of process (f, variant β).

The hydroxyethyl-cyclopropyl-azolyl derivatives of the formula (I)obtainable by the process according to the invention can be convertedinto acid addition salts or metal salt complexes.

In order to prepare acid addition salts of the compounds of the formula(I), those acids are preferred which have already been mentioned aspreferred acids in connection with the description of the acid additionsalts according to the invention.

The acid addition salts of the compounds of the formula (I) can beobtained in a simple manner by customary salt formation methods, forexample by dissolving a compound of the formula (I) in a suitable inertsolvent and adding the acid, for example hydrochloric acid, and areisolated in a known manner, for example by filtering off, and, ifappropriate, are purified by washing with an inert organic solvent.

In order to prepare metal salt complexes of the compounds of the formula(I), those salts of metals are preferred which have already beenmentioned as preferred metal salts in connection with the description ofthe metal salt complexes according to the invention

The metal salt complexes of the compounds of the formula (I) can beprepared in a simple manner by customary methods, for example bydissolving the metal salt in alcohol, for example ethanol and adding tocompounds of the formula (I). Metal salt complexes can be isolated in aknown manner, for example by filtering off, and if appropriate purifiedby recrystallization.

The active compounds according to the invention have a strongmicrobicidal action and can be employed as fungicides in plantprotection and in the protection of materials.

Fungicides are employed in plant protection for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Some causative organisms of fungal and bacterial diseases which comeunder the generic names listed above may be mentioned as examples, butnot by way of limitation:

Xanthomonas species, such as Xanthomonas oryzae;

Pseudomonas species, such as Pseudomonas lachrymans;

Erwinia species, such as Erwinia amylovora;

Pythium species, such as Pythium ultimum;

Phytophthora species, such as Phytophthora infestans;

Pseudoperonospora species, such as Pseudoperonospora humuli orPseudoperonospora cubense;

Plasmopara species, such as Plasmopara viticola;

Peronospora species, such as Peronospora pisi or P. brassicae;

Erysiphe species, such as Erysiphe graminis;

Sphaerotheca species, such as Sphaerotheca fuliginea;

Podosphaera species, such as Podosphaera leucotricha;

Venturia species, such as Venturia inaequalis;

Pyrenophora species, such as Pyrenophora teres or P. graminea (conidiaform: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as Cochliobolus sativus (conidia form:Drechslera, syn: Helminthosporium);

Uromyces species, such as Uromyces appendiculatus;

Puccinia species, such as Puccinia recondita;

Tilletio species, such as Tilletia caries;

Ustilago species, such as Ustilago nuda or Ustilago avenae;

Pellicularia species, such as Pellicularia sasakii;

Pyricularia species, such as Pyricularia oryzae;

Fusarium species, such as Fusarium culmorum;

Botrytis species, such as Botrytis cinerea;

Septoria species, such as Septoria nodorum;

Leptosphaeria species, such as Leptosphaeria nodorum;

Cercospora species, such as Cercospora canescens;

Alternaria species, such as Alternaria brassicae and

Pseudocercosporella species, such as Pseudocercosporellaherpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

The active compounds according to the invention are suitable in plantprotection, in particular, for combating cereal and rice diseases. Thus,powdery mildew and rust diseases, such as Erysiphe, Leptosphaerianodorum, Pyrenophora teres, Cochliobolus sativus and Fusarium nivale oncereals and also Pyricularia and Pellicularia on rice can beparticularly well combated. The substances can additionally be usedagainst Botrytis cinerea, true mildew on cucumbers and also againstVenturia on apples; they additionally have a very good in-vitro action.

In the protection of materials, the active compounds according to theinvention can be employed for the protection of industrial materials.Industrial materials are in this connection taken to mean non-livingmaterials which have been prepared for use in industry. For example,industrial materials which it is intended to protect from microbialchange or destruction by use of the active compounds according to theinvention can be adhesives, glues, paper, cardboard, textiles, leather,wood, paints, plastic articles, cooling lubricants and other materialswhich can be attacked or decomposed by microorganisms. In the context ofthe materials to be protected, parts of production plants, for examplecooling water circulations, may also be mentioned, which may be impairedby replication of microorganisms. In the context of the presentinvention, technical materials which may be mentioned are preferablyadhesives, glues, papers and cardboards, leather, wood, paints, coolinglubricants and cooling circulations, particularly preferably wood.

Microorganisms which may cause a degradation or a change in theindustrial materials may be, for example, bacteria, fungi, yeasts, algaeand slime organisms. The active compounds according to the inventionpreferably act against fungi, in particular Hyphomycetas,wood-discolouring and wood-destroying fungi (Basidiomycetes), and alsoagainst slime organisms and algae.

Microorganisms which may be mentioned are those of the following orders:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puteana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, such as Trichoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa,

Staphylocuccus, such as Staphylococcus aureus.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, suspensions, powders, foams, pastes,granules, aerosols, very fine capsules in polymeric substances and incoating compositions for seed, as well as ULV formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water. By liquefied gaseous extenders orcarriers are meant liquids which are gaseous at ambient temperature andunder atmospheric pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide. As solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly-disperse silica, alumina and silicates. Assolid carriers for granules there are suitable: for example crushed andfractionated natural minerals such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,corn cobs and tobacco stalks. As emulsifying and/or foam-forming agentsthere are suitable: for example non-ionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as albumin hydrolysis products. Asdispersing agents there are suitable: for example lignin-sulphite wasteliquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, moleybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in theformulations as a mixture with other known active compounds, such asfungicides, insecticides, acaricides and herbicides, as well as inmixtures with fertilizers and other growth regulators.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, emulsifiable concentrates, emulsions, foams, suspensions,wettable powders, pastes, soluble powders, dusts and granules. They areused in the customary manner, for example by watering, spraying,atomizing, scattering, dusting, foaming, brushing on and the like. It isfurthermore possible to apply the active compounds by the ultra-lowvolume method or to inject the active compound formulation or the activecompound itself into the soil. The seeds of the plants can also betreated.

When using the substances according to the invention as fungicides, theamounts applied can be varied within a relatively wide range dependingon the type of application. Thus, in the treatment of parts of plants,the active compound concentrations in the use forms are, in general,between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%. Inthe treatment of seed, amounts of active compound of 0.001 to 50 g perkilogram of seed, preferably 0.01 to 10 g, are generally required. Forthe treatment of soil, active compound concentrations of 0.00001 to 0.1%by weight, preferably 0.0001 to 0.02% by weight, are required at theplace of action.

The preparation and the use of the active compounds according to theinvention follows from the examples below.

PREPARATION EXAMPLES Example 1 ##STR36##

3.90 g (0.011 mole) of2-(1-chloro-cyclopropyl)-2-[4-(2-chloro-1,1,2-trifluoroethoxy)-phenylethenyl]oxiranein 20 ml of dimethylformamide are added dropwise to a solution warmed to80° C. of 2.96 g (0.043 mole) of 1,2,4-triazole and 0.48 g (0.0043 mole)of potassium tert.-butoxide in 30 ml of dimethylformamide. The reactionmixture is subsequently stirred for 12 hours at 80° C. and thenconcentrated by stripping off the solvent under reduced pressure. Theresidue is taken up in ethyl acetate, and the resulting solution iswashed three times with water, dried over sodium sulphate andconcentrated under reduced pressure. The residue which remains ischromatographed on a silica gel column using a mixture of cyclohexane:ethyl acetate =1:1. After evaporating the eluate, 3.2 g (69% of theory)of 2-(1-chlorocyclopropyl)-4-[4-(2-chloro-1,1,2-trifluoroethoxy)-phenyl]-1-(1,2,4-triazol-1-yl)-but-3-en-2-ol areobtained in the form of a solid substance of melting point 113°-118° C.

Preparation of Starting Materials ##STR37##

A solution of 6.35 g (0.031 mole) of trimethylsulphoxonium iodide in 20ml of dimethyl sulphoxide is added at -15° C. with stirring to asuspension of 0.75 g (0.031 mole) of sodium hydride in 25 ml of amixture of dimethyl sulphoxide: tetrahydrofuran =3:2. After warming thereaction mixture to 0° C., a solution of 9.6 g (0.028 mole) of1-chloro-cyclopropyl 4-(2-chloro-1,1,2-trifluoroethoxy)-phenyl-ethenylketone in 15 ml of dimethyl sulphoxide is added dropwise with stirring.The mixture is subsequently stirred at 0° C. for 15 minutes and at roomtemperature for 45 minutes. The reaction mixture is then poured into 100ml of ice water and the mixture is extracted three times withcyclohexane. The combined organic phases are washed once with water,dried over sodium sulphate and then concentrated under reduced pressure.8.89 g (89% of theory) of2-(1-chloro-cyclopropyl)-2-[4-(2-chloro-1,1,2-trifluoroethoxy)-phenylethenyl]-oxiraneare obtained in this way in the form of an oily product which is reactedfurther without additional purification. ##STR38##

0.6 g (0.011 mole) of potassium hydroxide powder is added at roomtemperature to a solution of 24.3 g (0.102 mole) of4-(2-chloro-1,1,2-trifluoroethoxy)-benzaldehyde and to 12.1 g (0.102mole) of 1-chloro-cyclopropyl methyl ketone in 100 ml of tetrahydrofuranand the mixture is then stirred at 40° to 50° C. for 8 hours. Thereaction mixture is then poured into a saturated aqueous ammoniumchloride solution and the mixture is extracted twice with cyclohexane.The combined organic phases are dried over sodium sulphate andconcentrated under reduced pressure. The residue which remains ischromatographed on silica gel using a mixture of cyclohexane:ethylacetate =10:1 as eluent. By evaporating the eluate, 17 g (49% of theory)of 1-chloro-cyclopropyl4-(2-chloro-1,1,2-trifluoroethoxy)-phenyl-ethenyl ketone are obtained inthe form of an oily product.

IR spectrum (CHCl₃): Bands at 1580, 1600 and 1670 cm⁻¹

Example 2 ##STR39##

10.71 g (0.054 mole) of2-(1-chloro-cyclopropyl)-2-(furan-2-yl-ethyl)-oxirane are added dropwisewith stirring to a solution heated to 80° C. of 10.43 g (0.151 mole) of1,2,4-triazole and 1.12 g (0.01 mole) of potassium tert.-butoxide in 80ml of dimethylformamide. The reaction mixture is subsequently stirred at80° C. for 6 hours and then concentrated by stripping off the solventunder reduced pressure. The residue which remains is taken up in ethylacetate, and the organic phase is washed twice with water, dried oversodium sulphate and concentrated under reduced pressure. The residuewhich remains is chromatographed on silica gel using a mixture ofcyclohexane: ethyl acetate 1:1 as eluent. After concentrating theeluate, 7.87 g (55% of theory) of2-(1-chloro-cyclopropyl)-4-furan-2-yl-ethyl)-1-(1,2,4-triazol-1-yl)-butan-2-olare obtained in the form of a solid substance of melting point 83°-86°C.

Preparation of Starting Materials ##STR40##

A solution of 11.3 g (0.055 mole) of trimethylsulphonium iodide in 50 mlof dimethyl sulphoxide is added dropwise with stirring to a suspensioncooled to -15° C. of 1.33 g (0.055 mole) of sodium hydride in 75 ml of amixture of dimethyl sulphoxide: tetrahydrofuran =1:2. After warming thereaction mixture to 0° C., a solution of 10.0 g (0.05 mole) of1-(chloro-cyclopropyl)-furan-2-yl-ethyl ketone in 20 ml of dimethylsulphoxide is added dropwise with stirring. The mixture is subsequentlystirred at 0° C. for 10 minutes and at room temperature for 1 hour. Thereaction mixture is then poured into iced water and the mixture isextracted three times with cyclohexane. The combined organic phases aredried over sodium sulphate and concentrated under reduced pressure.10.27 g (96% of theory) of2-(1-chloro-cyclopropyl)-2-(furan-2-yl-ethyl)-oxirane are obtained inthis way in the form of an oily product which is reacted further withoutadditional purification. ##STR41##

740 mg of tris-triphenylphosphine-rhodium chloride are added to a 0.3 1autoclave. After flushing the autoclave with nitrogen, an air-freesolution of 17 g of 1-chloro-cyclopropyl 4-(furan-2-yl-)-ethenyl ketonein 150 ml of toluene is added and the mixture is heated to 50° C. undera hydrogen pressure of 30 bar. The hydrogen pressure is kept between 50and 60 bar until the gas uptake is complete. The mixture is then allowedto react further for 1 hour. For working up, the solvent is stripped offunder reduced pressure. The residue which remains is chromatographed onsilica gel using dichloromethane as eluent. After evaporating theeluate, 14.7 g (86% of theory) of 1-chloro-cyclopropyl4-(furan-2-yl)-ethyl ketone are obtained in the form of an oily product.

¹ H-NMR spectrum (200 MHz, CDCl₃);

δ=1.35 (m, 2H); 1.65 (m, 2H); 2.9 (t, 2H); 3.2 (t, 2H); 6.0 (m,1H); 6.3(m, 1H); 7.3 (m, 1H). ##STR42##

0.95 g (0.017 mole) of potassium hydroxide powder is added at roomtemperature to a solution of 20.0 g (0.169 mole) of 1-chloro-cyclopropylmethyl ketone and 14.0 ml (0.169 mole) of furan-2-carbaldehyde in 100 mlof tetrahydrofuran and the mixture is stirred at room temperature for 18hours. The reaction mixture is poured into saturated aqueous ammoniumchloride solution and the mixture is extracted three times withcyclohexane. The combined organic phases are dried over sodium sulphateand concentrated under reduced pressure. 34.0 g (100% of theory) of1-chloro-cyclopropyl 4-(furan-2-yl)-ethenyl ketone are obtained in thisway in the form of an oil.

IR spectrum (film):

Bands at 1550, 1600 and 1680 cm⁻¹

Example 3 ##STR43##

47.0 g (0.18 mole) of1-chloro-2-(1-chlorocyclopropyl)-4-(thiophen-2-yl)-but-3-in-2-ol isadded to a suspension of 100 g (0.72 mole) of potassium carbonate and24.8 g (0.36 mole) of 1,2,4-triazole in 300 ml of acetone and themixture is heated under reflux for 2 hours. The solvent is then strippedoff under reduced pressure, and the residue which remains is taken up inwater and extracted three times with dichloromethane. The combinedorganic phases are dried over sodium sulphate and concentrated underreduced pressure. The residue which remains is chromatographed on silicagel using a mixture of cyclohexane/ethyl acetate =1:1 as eluent. Afterevaporating the eluate, 7.9 g (15% of theory) of2-(1-chlorocyclopropyl)-4-(thiophen-2-yl)-1-(1,2,4-triazol-1-yl)-3-butin-2-olare obtained in the form of an oily product.

¹ H-MR spectrum (200 MHz, CDCl₃):

δ=1.00-130 (m, 4H]; 4.78 (AB-System), 2H); 6.98 (m, 1H); 7.18 (m, 1H);7.30 (m, 1H); 7.96 (s, 1H); 8.36 (s, 1H).

Preparation of Starting Materials ##STR44##

22.2 g (0.203 mole) of ethyl bromide are slowly added to 4.9 g (0.203mole) of magnesium turnings in 100 ml of diethyl ether. After completionof the addition, the reaction mixture is heated under reflux for 30minutes and then cooled to room temperature, and a solution of 20 g(0.185 mole) of 2-thienylethine in 50 ml of diethyl ether issubsequently added dropwise with stirring. The mixture is heated underreflux for 1 hour and again cooled to room temperature. 28.3 g (0.185mole) of 1-chloro-cyclopropyl chloromethyl ketone are added dropwisewith stirring and the mixture is then heated under reflux for a further2 hours. After cooling to room temperature, the reaction mixture ispoured into a saturated aqueous ammonium chloride solution and themixture is extracted three times with diethyl ether. The combinedorganic phases are washed once with water, dried over sodium sulphateand concentrated under reduced pressure. 47.0 g (97% of theory) of1-chloro-2-(1-chlorocyclopropyl)-4-(thiophen-2-yl)-but-3-in-2-ol areobtained in this way in the form of an oil which is reacted furtherwithout additional purification.

Example 4 ##STR45##

2.26 g (0.013 mole) of 3-chloro-perbenzoic acid are added at 0° C. to asolution of 4.0 g (0.011 mole) of4-biphenyl-2-(1-chloro-cyclopropyl)-1-(1,2,4-triazol-1-yl)-but-3-en-2-ol in 50 ml of dichloromethane and the mixture is stirred at roomtemperature for 5 hours. The reaction mixture is then washed three timeswith semisaturated aqueous sodium carbonate solution, dried over sodiumsulphate and then concentrated under reduced pressure. The residue whichremains is chromatographed on silica gel using a mixture ofcyclohexane/ethyl acetate =1:1 as eluent. 2.7 g (64% of theory) of4-biphenyl-2-(1-chloro-cyclopropyl)-3,4-epoxy-1-(1,2,4-triazol-1-yl)butan-2-olare obtained in this way in the form of a solid having a melting pointof 250°-254° C.

The compounds of the formula ##STR46## shown in the following Table 1are also prepared according to the methods indicated in the precedingexamples.

                                      TABLE 1                                     __________________________________________________________________________                                                           Physical or            Example                                                                            Comp.                                             spectroscopic          No.  No  R.sup.2           Y        X R.sup.1          const.                 __________________________________________________________________________    5    I-5                                                                                ##STR47##        CHCH     N Cl               IR: 1700, 1730,                                                               3000-3400                                                                     cm.sup.-1              6    I-6                                                                                ##STR48##        CHCH     N Cl               IR: 1730, 3100-                                                               3500 cm.sup.-1         7    I-7                                                                                ##STR49##        CHCH     N Cl               IR:                                                                           1730, 3200-3400                                                               cm.sup.-1              8    I-8                                                                                ##STR50##        CHCH     N Cl               IR: 1600, 1630,                                                               3200-3400                                                                     cm.sup.-1              9    I-9                                                                                ##STR51##        CHCH     N Cl               IR: 1600, 1720,                                                               3200-3400                                                                     cm.sup.-1              10   I-10                                                                               ##STR52##        CH.sub.2 CH.sub.2                                                                      N Cl               IR:                                                                           1730, 3200-3400                                                               cm.sup.-1              11   I-11                                                                               ##STR53##        CHCH     N Cl               m.p. 51-53°                                                            C.                     12   I-12                                                                               ##STR54##        CHCH     N Cl               IR:                                                                           1730, 3200-3400                                                               cm.sup.-1              13   I-13                                                                               ##STR55##        CHCH     N Cl               IR: 1670, 1720,                                                               3200-3400                                                                     cm.sup.-1              14   I-14                                                                               ##STR56##        CHCH cis N Cl               IR: 1600, 1660,                                                               3200-3400                                                                     cm.sup.-1              15   I-15                                                                               ##STR57##        CHCH trans                                                                             N Cl               IR: 1600, 1720,                                                               3200-3400                                                                     cm.sup.-1              16   I-16                                                                               ##STR58##        CHCH     N Cl               m.p. 48-49°                                                            C.                     17   I-17                                                                               ##STR59##        CHCH     N Cl               IR: 1720 cm.sup.-1                                                            200-3400                                                                      cm.sup.-1              18   I-18                                                                               ##STR60##        CHCH     N                                                                                ##STR61##       IR: 1680, 1720,                                                               3200-3400                                                                     cm.sup.-1              19   I-19                                                                               ##STR62##        CHCH     N Cl               m.p. 87-88°                                                            C.                     20   I-20                                                                               ##STR63##        CHCH     N Cl               IR:                                                                           1700, 3200-3400                                                               cm.sup.-1              21   I-21                                                                               ##STR64##        CHCH     N Cl               m.p.                                                                          143-145°                                                               C.                     22   I-22                                                                               ##STR65##        CHCH     N Cl               m.p. 128°                                                              C.                     23   I-23                                                                               ##STR66##        CH.sub.2 CH.sub.2                                                                      N Cl               IR:                                                                           1730, 3200-3400                                                               cm.sup.-1              24   I-24                                                                               ##STR67##                                                                                       ##STR68##                                                                             N Cl               IR: 1600, 1720                                                                3200-3500              __________________________________________________________________________                                                           cm.sup.-1          

In the following are examples, the compounds of the formulae indicatedbelow were employed as Comparison Examples: ##STR69##

The comparison substances are known from EP-OS (European PublishedSpecification) 0,298,332.

Example A Erysiphe Test (Barley)/Protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are dusted with spores of Erysiphe graminisf.sp. hordei.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%, in order to promotethe development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, the compound (I-7) according to the invention shows asubstantially better activity than the comparison substances (A), (B)and (C).

Example B Cochliobolus Sativus Test (Barley)/Protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofCochliobolus sativus. The plants remain in an incubation cabin at 20° C.and 100% relative atmospheric humidity for 48 hours.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 7 days after the inoculation.

In this test, the compound (I-10) according to the invention shows asubstantially better activity than the comparison substances (D), (E)and (F).

Example C Leptosphaeria Nodorum Test (Wheat)/Protective/

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a spore suspension ofLeptosphaeria nodorum. The plants remain for 48 hours in an incubationcabin at 20° C. and at 100% relative atmospheric humidity.

The plants are placed in a greenhouse at a temperature of about 15° C.and a relative atmospheric humidity of about 80%.

Evaluation is effected 10 days after the inoculation.

In this test, for example, the substance (I-10) according to theinvention shows a substantially better activity than the comparisonsubstances (D), (F) and (G).

Moreover, in this test the compounds (I-1), (I-7), (I-8), (I-14),(I-19), (I-20) and (I-22) show a substantially better activity than thecomparison substance (H).

Example D Leptosphaeria Nodorum Test (Wheat)/Curative

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for curative activity, young plants are sprayed with a sporesuspension of Leptosphaeria nodorum. The plants remain for 48 hours inan incubation cabin at 20° C. and 100% relative atmospheric humidity.The plants are then sprayed with the active compound concentration untildew-moist.

The plants are placed in a greenhouse at a temperature of about 15° C.and a relative atmospheric humidity of about 80%.

Evaluation is effected 10 days after the inoculation.

In this test, the compound (I-7) according to the invention shows asubstantially better activity than the comparison substance (J).

Example E Pyrenophora Teres Test (Barley)/Protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofPyrenophora teres. The plants then remain in an incubation cabin at 20°C. and 100% relative atmospheric humidity for 48 hours.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 7 days after the inoculation.

In this test, the compounds (I-1) and (I-13) according to the inventionshow a substantially better activity than the comparison substances (B)and (K).

Example F Fusarium Nivale Test (Rye)/Seed Treatment

The active compounds are used as dry dressings. These are prepared byextending the particular active compound with a ground mineral to give afinely pulverulent mixture, which ensures uniform distribution on theseed surface.

To apply the dressing, the infected seed is shaken with the dressing ina closed glass flask for 3 minutes.

2 Batches of 100 grains of the rye are sown 1 cm deep in standard soiland are cultivated in a greenhouse at a temperature of about 10° C. anda relative atmospheric humidity of about 95%, in seed boxes which areexposed to light for 15 hours daily.

About 3 weeks after sowing, the plants are evaluated for symptoms ofsnow mold.

In this test, the compounds (I-1) and (I-7) according to the inventionshow a substantially better activity than the comparison substance (K).

Example G Venturia Test (Apple) / Curative

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for curative activity, young plants are inoculated with anaqueous conidia suspension of the apple scab causative organism(Venturia inaequalis). The plants remain in an incubation cabin at 20°C. and 100% relative atmospheric humidity for 1 day and are then placedin a greenhouse. After a given number of hours, the plants are sprayedwith the preparation of active compound until dripping wet.

The plants are then placed in a greenhouse at 20° C. and a relativeatmospheric humidity of about 70%.

Evaluation is carried out 12 days after the inoculation.

In this test, the compound (I-10) according to the invention shows asubstantially better action than the comparison substances (F) and (G).

Moreover, in this test the compounds (I-1), (I-7) and (I-8) show asubstantially better action than the comparison substances (B) and (K).

It will be appreciated that the instant specification and claims are setforth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:
 1. An oxirane of the formula ##STR70## in which R²represents furyl which is optionally substituted by furyl, or representsthe radical of the formula ##STR71## wherein R⁴ representsdifluoromethoxy, 1,1,2,2-tetrafluoroethoxy,1,1,2-trifluoro-2-chloro-ethoxy, formyl, methoximinomethyl,methoxycarbonyl or phenoxymethyl andR⁵ represents hydrogen, or R⁴ and R⁵are linked in the ortho-position and together represent --O--CH₂ --O--,or R² represents the radical of the formula ##STR72## and Y representsthe grouping --CH₂ --CH₂ --, --CH═CH-- or --C.tbd.C--.
 2. A compoundaccording to claim 1, wherein such compound is2-(1-chlorocyclopropyl)-2-[4-(2-chloro-1,1,2-trifluoroethoxy)-phenyl]-vinyl-oxiraneof the formula ##STR73##
 3. A compound according to claim 1, whereinsuch compound is2-(1-chlorocyclopropyl)-2-[4-(1,1,2,2-tetrafluoroethoxy)-phenyl]-vinyl-oxiraneof the formula ##STR74##
 4. A compound according to claim 1, whereinsuch compound is2-(1-chlorocyclopropyl)-2-[(5-difluoromethoxy)-naphth-1-yl]-vinyl-oxiraneof the formula ##STR75##
 5. A compound according to claim 1, whereinsuch compound is2-(1-chlorocyclopropyl)-2-(2,3-methylenedioxyphenyl-vinyl-oxirane of theformula ##STR76##
 6. A compound according to claim 1, wherein suchcompound is2-(1-chlorocyclopropyl)-2-[4-(1,1,2,2-tetrafluoroethoxy)-phenyl]-ethyl-oxiraneof the formula ##STR77##